An Introduction to the Program

FullProf
Comments on the Examples Kit:
=pub=divers=fullp=examples=prc dat:zip
of the anonymous ftp-area in the server
bali:saclay:cea:fr

Juan Rodrguez-Carvajal
Laboratoire Leon Brillouin (CEA-CNRS)
Tel: (33) 1 6908 3343, Fax: (33) 1 6908 8261
E-mail: juan@bali.saclay.cea.fr

May 10, 1997

 Preface:
These notes have been written to help the people starting to use the program
FullProf. They will constitute part of the future manual of the program. The
notes are not yet nished and the author apologize for the errors they content.
The description of the main control le MYFILE.pcr has been suppressed for
simplicity. The user can always look at the horrible text-le FULLPROF.INS
for details concerning all comments and references to MYFILE.pcr given in
these notes.
As stated in the disclaimer of FULLPROF.INS,
Powder diraction is becoming more and more powerful but FullProf
is not an automatic (black-box) program, as is usually found in sin-
gle crystal structure determination. No attempt has been made to
predict the behaviour of the program against bad input data. The
user must check his(her) data before claiming a misfunction of the
program.
So, a beginner cannot start to use the program without any background
in crystallography, magnetism, diraction physics and data analysis. Even an
expert in these elds can expericence diculties the rst time (or even the n-
th time!) he(her) use the program. An eort is presently being developed to
facilitate the use of FullProf. The author expects to have a GUI (Graphical
User Interface) prepared by the end of the next summer. This GUI will be
independent of the platform (it is being developed in Java) and should helps
considerably new users.
The notes begin with a short description of the way to obtain FullProf from
the anonymous ftp-area. They follow with a chapter where it is given a brief
description of the purpose of the program and the list of input and output les.
The second chapter is dedicated to the description of strategies for using the
program and the description of examples. The best way to start is using exam-
ples that work properly if the good parameters are provided to the program. To
that end a kit of examples has been istalled in an accessible area of the server
bali:saclay:cea:fr. This kit is in a single le called pcr dat:zip. This le must
be unzipped with the well known PKWARE software. The format of the les is
for a PC, but they can be converted easily to UNIX with an editor or with a
simple application like dos2unix.
In the third chapter the mathematical expresions used inside FullProf are writ-
ten and discussed brie y. At present the notes nish with the description of the
magnetic structure factor, Fourier coecients of the magnetic moments, etc...
In future releases everything concerned with data treatment in FullProf will
be included. For the moment the user can consult FULLPROF.INS for futher
details.

Juan Rodrguez-Carvajal
Saclay, 7 April 1997

1
 Availability of FullProf
The most recent version of FullProf is always in pub/divers/fullp of the
anonymous ftp-area of the LLB unix-cluster. Users interested in creating their
own subroutines to link with FULLP-library are asked to read the le fpreadme
in the above mentioned ftp-area. To access this area from the Internet, one has
to type in the local host the following commands:

 LocalPrompt> ftp 132.166.17.100 <cr> , or

 LocalPrompt> ftp bali.saclay.cea.fr <cr>

Answer with the word: anonymous , to the Login request and password. To
get, for instance, the le fpreadme the user should, after the ftp prompt, do:

From a UNIX host:

ftp>cd pub/divers/fullp <cr> -> Go to FullProf area

ftp>get fpreadme <cr> -> Obtain the document
ftp>bye <cr> -> Return to host

This should also work in modern Open-VMS systems but, from some VMS-
VAX hosts:
ftp>set def "pub/divers/fullp" <cr> -> Go to FullProf area
ftp>get "fpreadme" <cr> -> Obtain the document
ftp>ex <cr> -> Return to host

Experienced users of ftp can go directly to the subdirectories and get the
les they want. The structure of subdirectories match the dierent platforms in
which FullProf can be run. Details are given in the le fpreadme. Recently
the anonymous ftp-area can be accessed via the WEB through the URL of the
LLB:

http://www-llb.cea.fr
It is of capital importance to have a plot program in order to visualize the
observed versus calculated powder pattern and their dierence. Such a program
is not included at present in the FullProf executable code. Dierent free-ware,
share-ware, or commercial programs can be user for this task. On the PC
(under DOS) a very useful program is PLOTR (written by Thierry Roisnel at
the LLB). PLOTR can be obtained in the same ftp-area as FullProf in the
directory pub/divers/plotr.

2
Chapter 1

GENERAL INFORMATION
ON FullProf
1.1 Purpose, references and documentation
The program is mainly developed for Rietveld analysis [1, 2] (structure pro-
le renement) of neutron (nuclear and magnetic scattering) or X-ray powder
diraction data collected at constant step in scattering angle 2 [4, 5]. The
program can be also used as a Prole Matching tool, without the knowlegde
of the structure. Single Crystal renements can also be performed alone or
in combination with powder data. Time-of- ight (TOF) neutron data analysis
will be available in future versions.
The program FullProf is based on the code of the DBW program, which, in
turn, is also a major modication of the original Rietveld-Hewat program. An
early version is discussed in the Young and Wiles article published in [6] and
described in the user's guide distributed by R.A. Young. The program FullProf
was developed starting with the code DBW3.2S (Versions 8711 and 8804), but it
has been so much modied that only the name and some basic subroutines keep
their original form. However, the main control input le created for use with
DBW (and DBWS) program can be used by FullProf with minor modications.
This le is accepted by FullProf which read it in interpreted free format. The
le generated, at the end of a run, by FullProf cannot be read by DBWS. The
le can content comments starting with the symbol ! in the rst position of
a line. These comments are useful for remembering the name of variables and
ags and greatly simplify the use of the program.
The source is written in standard FORTRAN 77 language, and is organized
as to be easily adapted to dierent computers. The present version can be run
under VMS, Open-VMS, Unix, MacOS and DOS-Windows (Lahey Computer
Systems Inc. FORTRAN-compiler, minimum 386/4Mb with co-processor re-
quired). The transformation of the source code to Fortran 90 is projected for
the future. The future version 4.0 will work with allocatable arrays, so that the
dimensions of arrays can be directly controlled by the user at run time.

3
1.2 Features of FullProf
Some of the most important features of FullProf are summarized below:
 Choice of peak shape (Gaussian, Lorentzian, modied Lorentzians, pseudo-
Voigt, Pearson-VII, Thompson-Cox-Hastings, numerical) for each phase
 Neutron and X-ray (laboratory and synchrotron sources)
 One or two wavelengths (eventually with dierent prole parameters)
 Background: xed, renable, adaptable, or with Fourier ltering
 Multi-phase (up to 8 phases)
 Preferred orientation : two functions available
 Absorption correction for cylinder and at plate sample shape.
 Choice between three weighting schemes: standard least squares, maxi-
mum likelihood and unit weights.
 Choice between automatic generation of hkl and/or symmetry operators
and le given by user.
 Magnetic structure renement (crystallographic and spherical representa-
tion of the magnetic moments). Two methods: describing the magnetic
structure in the magnetic unit cell of making use of the propagation vec-
tors using the crystallographic cell. This second method is necessary for
incommesurate magnetic structures.
 Automatic generation of re ections for an incommensurate structure with
up to 24 propagation vectors. Renement of propagation vectors in re-
ciprocal lattice units
 hkl-dependence FWHM for strain and size eects
 hkl-dependence of shift and asymmetry for special kind of defects
 Prole Matching. The full prole can be tted without prior knowledge
of the structure (needs only good starting cell and prole parameters)
 Quantitative analysis without need of structure factor calculations.
 Chemical(distances) and magnetic(magnetic moments) slack constraints
 Resolution function (Voigt function) may be supplied in a le
 Structural or magnetic model could be supplied by an external subroutine
for special purposes (rigid body, TLS, polymers, form factor renements,
small angle scattering of amphilic crystals, description of incommensu-
rate structures in real direct space, etc.)

4
  Single crystal data or integrated intensities can be used as observations
(alone or in combination with a powder prole)
 Neutron (or X-rays) powder patterns can be mixed with integrated inten-
sities of X-rays (or neutron) from single crystal or powder data
 Montecarlo search of starting parameters in a user-dened box for inte-
grated intensity data

1.3 Running the program, input and output les

To run the program the user has to invoke the name of the executable le or
an appropriate alias, for instance:
FULLPROF <cr>, or FullProf <cr>, or Fp <cr>...etc

Of course, the executable le must be placed in an accessible path.

FullProf can also be run from a command le. After invoking the execution
of the program the following dialog appears in the current window:

*******************************************************
*** PROGRAM FULLPROF (Version 3.2 - Jan97-LLB JRC) ***
*******************************************************
Rietveld, Profile Matching & Integrated Intensity
Refinement of X-ray and/or Neutron Data
(PC-version)

==> Give the code of the files (xx for xx.pcr):

After entering a value for xx, hereafter assumed to be CODFIL, the pro-
gram prompts the following question 1 :

==> Give the name of data file (yy for yy.dat)

( or yy.uxd, yy.acq)
(<cr> = CODFIL ):

If the user answer with <cr> the name of the data le is CODFIL.dat (or
CODFIL.uxd). We assume, in the following, the user has attributed the value
FILE to the item yy. The le CODFIL.pcr must be created (from the scratch
1
If xx=starting, the program enter in a new dialog to create an example of CODFIL.pcr
le (called starting:pcr) for making a pattern calculation. The user can modify this generated
le to adapt it to his(her) own problem

5
or by modifying an existing one) with the help of an ASCII editor. This le
contents the diraction conditions and crystallographic information needed by
the program. The optional le FILE.dat (or FILE.uxd, FILE.acq) contents the
prole intensity of the powder diraction pattern.
For doing sequential renements the user can run the program using a com-
mand le, or answer CYC to the prompt asking for the code of the les. In the
last case another dialog opens:
==> Code of the starting *.pcr file (xx for xx.pcr):

Here the user should answer with the xx explicit name (let us assume that
the code is CODFIL).

==> Give the code of data files (yy for yynnn.dat,uxd,acq)

(<cr> = CODFIL ):

As suggested by the question the name of the data les should have a part
that constitutes the code followed by a ordinal number. The user should give
here the code. Let us assume that the code is FILEDAT.
==> Number of the starting *.dat file: 46
==> Number of the last *.dat file: 133

The user should give the ordinal numbers of the rst and last les to be
processed. The numbers 46 and 133 are examples. The program works by
using the le CODFIL.pcr to process the le FILEDAT46.dat. The updated
CODFIL.pcr are, then, used to process the le FILEDAT47.dat, etc... At the
end, when the le FILEDAT133.dat has been processed, the control le contents
the parameters adequate to the last treated le. The results of the whole set of
treatments are stored in le CODFIL.RPA.
1.3.1 Input les
There are some references to names of control variables in this and the fol-
lowing sections. The precise meaning of these variables is described in FULL-
PROF.INS.
CODFIL.pcr (unit i Pcr)
Input control le. It must be in the current directory to run the
program. This le contains the title and crystallographic data of
the problem to be treated and must be prepared by user with a le
editor. There are two dierent formats for this le: the rst one is
free format and closely related to that of the DBWS program. The
second is based on keywords and commands 2 .
2
This last format is not available at present

6
 Warning! this le is normally up-dated every time you run the program
(see parameter NXT on LINE 3). In the rst stages of a renement, it is wise
to save a copy of this le with a dierent name.
The complete description of the le CODFIL.pcr is given in the manual of
the program. This is, at present, in the text-le FULLPROF.INS of the anony-
mous ftp-area: =pub=divers=fullp=doc= of the server bali:saclay:cea:fr.
The following les are optional:
FILE.dat (unit i Dat)
Intensity data le, its format depends on instrument. If you do not
specify the name FILE, the program takes FILE=CODFIL. Not
necessary for pattern calculation modes.
FILE.bac (unit i Bac)
Background le. This le can also be generated by the program.
The format of this le is the same as that of FILE.DAT for IN-
STRM=0:
 rst line : 2(initial) step 2(nal), any comment
 following lines: list of intensities in free format.
CODFILn.hkl or hkln.hkl
Set of les with the re ections corresponding to phase n (n is the
ordinal number of a phase). These les are optional and depend on
the value of the parameter IRF(n). This le can also be generated
by the program.
MYRESOL.inst
File describing the instrumental resolution function. Any legal le-
name can be used and its content depend on the value of the pa-
rameter IRESO.
global.shp or CODFIL.shp
File providing a numerical table for calculating the peak shape and
its derivative. The peak shape should be given in a normalized form
R x 2 [x1; x2] is chosen to give a FWHM=1
P (x) where the variable
and the area is 1, so xx12 P (x)dx = 1. That allows the use of the con-
ventional U,V,W parameters for dening the FWHM as a function
of angle.
The format of this le is the following:
 Line1: Any comment
 Line2: Np8; nupr; 21; 22; :::2nupr
7
 { Np8 : Number of points
{ nupr : Number of dierent proles
{ 2j : Angle to which prole j is best adapted
The rest of the lines are columns with x; P1(x); P10 (x); P2(x); P20 (x);
0 (x) in free format. P 0 (x) is the derivative of Pj (x) with respect
:::Pnupr (x); Pnupr j
to x. The prole of a re ection situated between 2j and 2j +1 is linearly
interpolated between the proles Pj (x) and Pj +1 (x).
CODFIL.cor
User-dened intensity corrections. The corrections are applied to
the integrated intensities as a multiplicative constant. The le COD-
FIL.cor starts with a comment and a list of pairs: Scattering Vari-
able - Correction
1.3.2 Output les
Except for CODFIL.out and CODFIL.sum, their creation depends on the value
of a ag which is quoted in parenthesis. The short name of the ag (controlling
the output) used in the commented pcr-le is given in brackets.
CODFIL.out (unit i Out) 3
This is the main output le which contains all control variables and
rened parameters.
CODFIL.prf (unit i Prf)
Observed and calculated prole : to be fed into PLOTPOW, PLOTR,
...(if IPL2 [Prf] dierent from zero)
CODFIL.rpa (unit i Rpa)
Summary of rened parameters. Short version of CODFIL.SUM (if
JCIL=1)
CODFIL.sym (unit i Sym)
List of symmetry operators (if IPL1=JSY=1)
The last two les are necessary to run DISTAN or BONDSTR
CODFIL.sum (unit i Sum)
Parameter list after last cycle: summary of the last parameters,
their standard deviations and reliability factors. An analysis of the
goodness of the renement is included at the end if IANALY=1.
CODFIL.fou (unit i Fou)
(If JFOU=1)
3
The actual numbers of the logical units for input-output les are given in le FUL0.inc

8
 h; k; l, Structure Factors in Cambridge format to be fed
into FOURTK (FOURPL) to produce Fourier maps. It
corresponds to the le usually called HKLFF.DAT but
you must prepare the second le CRYST.cry.
(If JFOU=2)
List of 'observed' structure factors in SHELXS format
h; k; l; Fobs; (Fobs) (3I4,2F8.2)
CODFILn.shx
If JFOU=2, template of SHELXS *.IN le.
CODFILn.hkl
Files that can be input or output les. Depending on the value of
IRF(n)
CODFIL.hkl (unit i hkl)
Complete list of re ections of each phase.
 JLKH=1
) If JOBTYP<2
Code, h; k; l; mul; dhkl; 2; FWHM; Iobs ; Icalc; Iobs
Icalc .
) If JOBTYP >1
h; k; l; mult; Icalc; 2; dhkl
 JLKH=2
 ) Output for SIRPOW92
h; k; l; mul; sin=; 2; Fwhm; F 2; (F 2)
 JLKH=3
{ ) Output of real and imaginary part of structure
factors (only for crystal structures)
h; k; l; mult; Freal; Fimag; 2; Intensity
(the obtained le can be used as a CODFILn.HKL le for new runs)
CODFIL.sav (if JCIL=2)
List of re ections between two selected angles
h; k; l; mult; Iobs; 2; dhkl

9
Chapter 2

THE RIETVELD METHOD

IN PRACTICE
In this chapter some simple rules for starting a Rietveld renement are stated.
After discussing some of these rules and comment about the problems the user
can experience in running the program, a short description of the examples given
in the le pcr dat:zip is given. The examples treated in this chapter are quite
simple. Experienced users can apply other techniques and more sophisticated
sets of parameters of peak shapes that are not discussed here.

2.1 Rietveld renement

Although the principles behind the Rietveld prole renement method are
rather simple, the use of the technique requires some expertize. This results
merely from the fact that Rietveld renement uses a least-squares minimization
technique which as any local search technique gets easily stuck in false minima.
Besides, correlation between model parameters may easily cause divergence in
early stages of the renement. All these diculties can actually be readily
overcome by following a few simple prescriptions:
 Use the best possible starting model: this can be easily done for back-
ground parameters and lattice constants. In some cases, in particular
when the structural model is very crude, it is advisable to analyse rst
the pattern with the total pattern tting (prole matching) algorithm in
order to determine accurately the prole shape function, background and
cell parameters before running the Rietveld method.
 Do not start by rening all structural parameters at the same time. Some
of them aect strongly the residuals (they must be rened rst) while
others produce only little improvement and should be held xed till the
latest stages of the analysis.
 Before you start, collect all the information available both on your sample
(approximate cell parameters and atomic positions) and on the dirac-
tometer and experimental conditions of the data measurement: zeroshift

10
 and resolution function of the instrument, for instance. Then a sensible
sequence of renement of a crystal structure, using X-ray diraction, is
the following:
1. scale factor
2. scale factor, zero point of detector , 1rst background parameter and
lattice constants (in case of very sloppy background, it may be wise
to actually rene at least two background parameters)
3. same + atomic positions + overall Debye-Waller factor (especially
for low or high temperature data)
4. same + peak shape function (PSF) and asymmetry parameters
5. same + atom occupancies (if required)
6. same + individual isotropic thermal parameters (Debye-Waller)
7. same + individual anisotropic thermal parameters (if justied)
To nish up, you may wish to rene also:
8. additional background parameters
9. the parameters SYCOS and SYSIN (line 10-1) to correct for instru-
mental or physical 2 aberrations with a COS or SIN angular depen-
dence.
In all cases, it is essential to plot frequently the observed and experimental
patterns: examination of the dierence pattern is a quick and ecient method
to detect blunders in the model or in the input le which controls the rene-
ment process and may also provide useful hints on the best sequence, to follow
to rene the whole set of model parameters.
When large and unrealistic uctuations of certain parameters occur from one
cycle to the next, examine the correlation matrix: if large values (say larger than
50%) are observed, rene separately the corresponding parameters, at least in
the early stages of the renement.
Finally it must be remembered that there is a limit to the amount of informa-
tion that can be retrieved from a powder diraction pattern. Indeed structures
with up to a hundred or more structural parameters can be rened from neu-
tron powder data but such renements must be performed with great care; for
renements involving a large number of variables the physical signicance of
certain parameters must be carefully examined. For instance thermal and PSF
parameters can become poorly dened and act as a dumping ground for sys-
tematic errors. In such cases it is preferable to x their values to a physically
reasonable number and exclude them from the renement.
When the uncertainty concerns the atomic parameters, it may help to provide
some external information to the program. This can be achieved for instance by
using strict constraints: for instance the displacement (thermal) parameters of
chemically similar but crystallographically distinct atoms may be constrained
to be identical, or the occupancy of two distinct and partly occupied sites of a
structure may be compelled by the chemical analysis of the material.

11
2.2 Total-pattern tting (Prole Matching)
This procedure does not require any structural information except approximate
cell parameters. This makes the data input much simpler and enlarges consid-
erably the eld of application of powder pattern prole renement. However
the constraints applied to the renement are far less severe than for Rietveld
renement and total-pattern tting is thereby more prone to instabilities. This
renement mode can be used in two ways:
1. Prole Matching with constant scale factor (JBT=2). In this mode the
scale factor is not allowed to vary and intensities are rened individually
using, iteratively, the Rietveld formula for getting the observed integrated
intensities. The recommended procedure is as follows:
 For the rst renement, set IRF(n) of the phase n undergoing prole
matching to 0 and the number of rened parameters (maxs on line
9) to zero. Run FullProf for a few (say 10) cycles. This will set up
the hkl's and intensity le CODFILn.hkl.
 If the result of the above step is satisfactory (see plot!), rename the
le CODFIL.new to CODFIL.pcr, or use directly CODFIL.pcr if it
was automatically updated. Edit the new CODFIL.pcr le to select
the parameters to rene. The progression of the renement is very
similar to that used for Rietveld renement: zero point of detector,
1rst background parameter and lattice constants.
In this mode of renenent FullProf cannot calculate theoretical line inten-
sities and all hkl values permitted by the space group are considered and
included in the renement... which sometimes means a lot of re ections!.
Using this type of renement one has to bear in mind that the starting
cell parameters and resolution function determines to a large extend the
obtained intensity parameters. One cannot expect to rene properly the
cell parameters of a compound with a severe overlap of re ections if the
starting parameters are of poor reliability. It is wise to start with low an-
gle re ections (without rening the FWHM parameters) and progressively
increase the angular domain.
2. Prole Matching with constant relative intensities (JBT=3). In this mode
the intensities are held xed and only the scale factor is varied. Since WPF
does not require the calculation of the structure factors it runs faster than
Rietveld renement.

2.3 Hints'n tricks

Even if you follow carefully the recommendations mentioned above, you may
experience diculties to rene your data; most of them can be avoided by
following a few simple rules:

12
  If the number of measured re ections is limited, select carefully the rened
parameters and keep the others xed to physically reasonable values (for
instance rene the overall displacement (temperature) parameters, not
the individual ones).
 Exclude regions where the background is strongly distorted if any (e.g.
background from sample environment may show odd variations) for the
background function used in the code may not be able to cope with it.
 Look carefully for the values of the standard prole parameters of the
instrument used for getting the data. If, for any reason, you do not know
the shape of the diraction proles, start with pure gaussian, i.e. use
rst NPROF=0 on line 2. In the nal stages of renement examine the
dierence prole to look for departure from a gaussian shape and change
to pseudo-Voigt (rst with a small  value) if required. If the value of  is
much larger than zero, remember to increase the range of the calculated
prole (WDT on line 4); failure to increase properly this parameter will
lead to discontinuities in the edges of the calculated prole.
 The prole parameters are sometimes dicult to rene especially for data
spanning only a limited angular range or samples giving broad diraction
lines. In such case, it is normally advisable to x one or more FWHM
parameter or to constraint their variation with a proper use of the code-
words. As prole parameters may vary from sample to sample (strain
and/or size broadening) and depend from instrumental set-ups, you must,
at some stage, rene U, V and W from your own data.
The best method is of course to rene rst a standard pattern with no
sample broadening in order to determine the U, V, W parameters of your
instrument.

2.4 Trouble shooting

 If you experience diculties from the very beginning (for instance a sin-
gular matrix at the rst renement), start rening the scale factor only
and examine the dierence pattern with a plotting program. This will
most of the time reveal a glaring blunder in the input data (zero-shift,
step size, angular limits etc).
 Owing to the complexity of the control le, error messages given in the
terminal are not always easy to decipher in that they do not necessarily
point to the initial error but merely to one of its consequences. Most of
the time, run time errors result from an error in the sequence of lines in
the control le, e.g., an inadequacy between the number of atoms stated
on line 11.2 and the number of atomic positions given on lines 11.4. Look
at the output le CODFIL.OUT to verify if the dierent items have been
properly read by the program.
 Errors in the generation of hkl have been observed for a few space groups:
check carefully your list of re ections at the end of le CODFIL.out.

13
2.5 Examples. Content of pcr dat:zip
To test the installation of the program, or for training purposes, a list of com-
plete examples are provided together with FullProf. The le pcr dat:zip can
be obtained by anonymous ftp to the server bali:saclay:cea:fr in the area
=pub=divers=fullp=examples. Set the mode to binary in order to get prop-
erly the le. This le must be unzipped with PKUNZIP under Windows or
DOS. The format of the les is for DOS, so they have to be converted to other
platforms using the appropriate utility. Among the les obtained after a suc-
cessful unzip that called PCR READ.ME gives an explanation of the whole set
of les inside pcr dat:zip from the point of view of an installation test. This
le is displayed below:
CONTENT of PCR_DAT.ZIP (February 1997)

1:The files contained in pcr_dat.zip can be used for testing FullProf.

They have been selected in order to illustrate the use of FullProf in
a variety of situations. In no way the proposed models pretend to be
the most adequate to the data. In some cases there is a clear
disagreement between the data and the model.

2:For a quit test under DOS or under UNIX the user can type at the
command line:
fullprof_alias < tempo.inp

FullProf will be executed for all files existing in file: tempo.inp

where the answers expected by FullProf are collected.

3:The files are in PC format. They have to be converted to UNIX, Mac,

or VMS using one of the appropriate utility (dos2unix, editor,...).

4:The number and nature of files can change with different releases.

At present the files are:

PCR code Purpose Data File

--------------------------------------------------------------------
c60 : compares C60 x-tal data to form-factor sin(Qr)/Qr: c60.int
ce1 : refinement of a CeO2 standard : ceo2.dat
ce2 : " : "
dy : Four different ways of refining the crystal : dy.dat
dya : and magnetic structure of DyMn6Ge6 : "
dyb : : "
dyc : : "
hobb : Refinement with integrated intensities (Nuc+mag) : hobb.int
hob : Montecarlo search for mag. moments in Ho2BaNiO5 : "
hobk1 : Three different ways of refining the crystal : hobk.dat

14
 hobk2 : and magnetic structure of Ho2BaNiO5 : "
hobk3 : : "
la : Two ways for strain refinement in La2NiO4 : la.dat
lab : with low resolution neutron powder data. : "
monte : Montecarlo test with single crystal data : monte.int
pb : Profile matching test of PbSO4 neutron data : pbso4.dat
pbso4 : Crystal structure refinement of PbSO4 : "
pbso4a: " (anisotropic b's) : "
hmt : Rigid body refinement of simulated data : hmt.dat
urea : Test Rigid body with satellites (simulated data): urea.dat
ycbacu: YBaCuO with Ca. Data from D1A : ycbacu.dat

In general, the user must rst run the program to verify that the provided
pcr-les behave correctly. After that, the user should make a copy of the con-
trol les for saving them before running his(her) own options. The best way
is to modify the given values for dierent sets of parameters and run the pro-
gram. The beginner must make extensive use of editor-plot cycles. The plot of
the le CODFIL.prf is of absolutely necessity for knowing the behaviour of the
program under bad (or inaccurate) input parameters.
To use the above les for training, the unexperienced user must start with
the most simple cases, that is ce1.pcr and ce2.pcr used to process the le
ceo2.dat. This le corresponds to a data collection on cerium oxide with a
good laboratory X-ray powder diractometer, using CuK doublets.
The next les to be processed are those of PbSO4 . The data le correspond
to neutron powder diraction on D1A (ILL) that was used in a Round Robin
on Rieveld renement (R.J. Hill (1992), J.Appl.Cryst 25, 589 ). For people
working mainly with crystal structures the next les to be studied are: ycbacu,
hmt, urea for powder diraction.
Some les for single crystal data are also given: c60, monte. The rst one use
a too simplistic model (just a spherical shell) for describing the C60 molecule
that give poor results. The user can try this le as an example of special form
factor renement. The free parameters are the radius of the C60 molecule and
its isotropic temperature factor. The le monte correspond to an articial use
of the Montecarlo technique for searching a starting set of initial parameters.
Data are from neutron diraction on a single crystal of oxidized Pr2 NiO4+ .
People interested in magnetic structures can use the rest of the les in the
following order.
 la, lab: renement of the low temperature phase crystal and magnetic
structure of La2 NiO4 . The data are from a medium-low resolution neutron
powder diractometer (D1B at ILL). This phase present a microstrain
that is rened using two equivalent methods in the two les. The magnetic

15
 structure is very simple. A peak from an impurity phase is near the rst
magnetic peak.
 The les hobb, hob, hobk1, hobk2, hobk3 concern the renement of
the crystal and magnetic structures of Ho2 BaNiO5 at 1.5K, using dierent
methods and conditions. The user can verify that hob.pcr can solve
the magnetic structure of Ho2 BaNiO5 just testing random congurations.
This is a very favourable case and this method cannot be applied for
general magnetic structure determination. The data are from D1B.
 The les dy, dya, dyb, dyc use dierent methods to rene the incon-
mensurate magnetic structure of DyMn6 Ge6. This is a conical structure
that can be rened using a real space approach as in dy and dya or using
Fourier components of the magnetic moments, which is the general for-
malism of FullProf for handling magnetic structures. This is the case of
les dyb and dyc
The only right way to learn about crystal and magnetic structure rene-
ments is practicing with real data as these are. However, it is better when the
user try with its own data on a problem of interest to him(her).

16
Chapter 3

MATHEMATICAL
INFORMATION
In this chapter the basic equations concerned with the calculations performed
in FullProf are discussed. It is supposed that the reader has a good knowl-
edge of powder diraction, so the explanations given below concern mainly the
description of the terms involved in the formulae. The references to numbered
lines (eg. LINE 3, Line 11-4-1) correspond to lines of the main input control
le CODFIL.pcr described in FULLPROF.INS.

3.1 Calculated prole

A powder diraction pattern can be recorded in numerical form for a discrete set
of scattering angles, times of ight or energies. We will refer to this scattering
variable as T . Then, the experimental powder diraction pattern is usually
given as two arrays fTi; yi gi=1;::n. In FullProf the array fTig is not actually
stored because it is supposed that the values of the scattering variable are
equally spaced 1 :
Ti = Tinit + (i 1)STEP
The prole can be modeled using the calculated counts yci at the ith step by
summing the contribution from neighbouring Bragg re ections plus the back-
ground: X X
yci = S I;h
(Ti T;h ) + ybi (3.1)
 h
The vector h( = H, or = H+k) labels the Bragg re ections, the subscript 
labels the phase and vary from 1 up to the number of phases existing in the
model. In FullProf the term phase is sinonymous of a same procedure for
calculating the integrated intensities I;h .
I;h = fLF 2 ATPC g;h (3.2)
1
In some cases the program can trasform internally the data to constant step by making
the appropriate interpolation

17
For simplicity we will drop the -index. Sometimes we will refer to the whole
arrays fyi g and fyci g as yobs and ycal respectively. The meaning of the dierent
terms appearing in 3.1 and 3.2 is the following:
 S is the scale factor of the phase 
 Lh contains the Lorentz, polarization and multiplicity factors.
 Fh is the structure factor.2
 Ah is the asymmetry function
 Th is the transmission factor
 Ph is the preferred orientation function

is the re ection prole function that models both instrumental and
sample eects.
 C is a user-dened correction
 ybi is the background intensity
In the following sections we discussed the dierent terms in more detail.

3.2 Background
The background intensity ybi at the ith step is obtained (see LINE 2 and LINE
6* or Line 10-2*) either from an user-supplied table of background intensities,
or from a renable background function:
X5 Ti X 6
ybi = Bm ( BKPOS 1)m + BCj sin(QQdi dj ) (3.3)
m=0 j =1 i j
The origin of the background polynomial is given by a selectable input
parameter BKPOS (LINE 4) and should be supplied by the user. The sec-
ond sum is used only if NBCKGR=-1. The parameters to be rened are:
B0 ; B1 ; :::B5; BC 1 ; :::BC 6; d1; :::d6. Qi is the modulus of the scattering vector
(Q=2 h) at the ith step, and is given by:
i Q = 4 sin i
 (3.4)
where  = 1 (rst wavelength) in FullProf. The parameters dj are distances
in 
A.
The background can be also read from a supplied le FILE.bac. The ac-
tual background is calculated from the read background applying the following
formula:
Background(2) = b1BackgRead[(1 + b3 )2 + b4] + b2 (3.5)
2
The ratio of the intensities for the two wavelengths handled by the program is absorbed
in the calculation of Fh2 , so that only a single scale factor is required.

18
The background parameters and codes, given in Line 10-2*, correspond to the
coecients of the above formula in the order: b1; b2; b3; b4. If b1 is given as
zero, the program puts b1 =1. Limits against divergence are xed by program.
The parameter b3 is allowed to vary up to a maximum value ABS(b3)=0.1 and
ABS(b4) is kept below 3 degrees (2). The user can chek the excursion of
those parameters out of the allowed range when they are strictly zero and their
standard deviation is (xed arbitrarily to) 0.99999. This option is useful when
complicated background shapes are present due to sample environment.
Another procedure for treating the background has been introduced. The
background is ajusted iteratively at each cycle by using a Fourier ltering tech-
nique. The starting background is read from the le FILE.bac. At cycle n the
new background is calculated from the old one, cycle n 1, with the formula:
Background(n) = Background(n 1) + Filtered[yobs ycal](n 1) (3.6)
where Filtered[yobs ycal ] is a strongly smoothed version of yobs ycal . The
parameter controlling the smoothing is FWINDOW which is equivalent to PST
described in subroutine SMOOFT described in Numerical Recipes (see [23]).
The implementation of SMOOFT in FullProf is not the same as in [23]. When
using this method it is wise to draw the nal background to see if it is really a
smooth curve. This option is only justiable in cases of a very wavy background.
The starting background should be close to the real one.

3.3 Peak-shape functions

The prole function
is selected by the control variable NPROFR(LINE 2). All
the prole functions used in FullProf are normalized to 1 (i.e. +1 1
(x)dx =
1). The variable is x = T Th , the FWHM will be called H . The denition
of
i (x), where the subscript i stands for the value of the variable NPROF, is
the following:
GAUSSIAN:
0(x) = G(x) = aG exp( bG x2 ) (3.7)
where: s
2
aG = H ln2 bG = 4Hln22
LORENTZIAN:
1 (x) = L(x) = 1 +abL x2 (3.8)
L
where:
2
aL = H bL = H42
MODIFIED LORENTZIAN:
2 (x) = ML(x) = (1 + abML x2)2 (3.9)
ML
where: qp p
4 2 1
aML = bML = 4( 2 1)
H H2

19
 INTERMEDIATE LORENTZIAN:
3(x) = IL(x) = aIL (3.10)
(1 + bIL x2 )3=2
where: p 2=3
aIL = 2 1 b = 4(22=3 1)
H IL H2
PEARSON VII:
6(x) = PV II (x) = (1 + ab V II x2 )m (3.11)
V II
where: p 1=m
(m )
aV II = (m) 1=2 p2 2 1 b = 4(21=m 1)
H V II H2
PSEUDO-VOIGT:
5 (x) =
7(x) = pV (x) = L0(x)+(1  )G0(x) 01
(3.12)
0
The pV (x) function is a linear combination of a lorentzian (L ) and a gaussian
(G0) of the same FWHM (H ) 3 . The prole function NPROF=4,
4 (x), is
a superposition of three pV (x) functions (see below 3.21). The dierence be-
tween NPROF=5 and NPROF=7 is that in the later the parameter  is not
directly renable but calculated from HL and HG Let us precise this point. The
pseudo-Voigt function is an approximation to the Voigt function dened as the
convolution of a lorentzian and a gaussian:
Z +1
VOIGT: V (x) = L(x)
G(x) = L(x u)G(u)du (3.13)
1
where L(x) and G(x) have dierent FWHM (HL and HG , respectively). The
pV (x) function is an approximation that substitutes the two shape parameters
HL and HG by the pair (; H ). The Voigt function can be written in a closed
form in terms of the complex error function and the integral breaths of the
Lorentzian (L) and Gaussian components (G ):
" p !#
1
V (x) = G Re erf  j x j +i  p  L (3.14)
G G
where: Zx
erf (x) = p2 e t2 dt
0
Numerically is more easy to calculate the pseudo-Voigt approximation 3.12
using a numerical approximation relating the pairs (HL; HG ) and (; H ) (see
[]):
H 5 = (HG5 +2:69269HG4 HL+2:42843HG3 HL2 +4:47163HG2 HL3 +0:07842HGHL4 +HL5 )
 2  3 (3.15)
 = 1:36603 HHL 0:47719 HHL + 0:11116 HHL (3.16)
3
The reader can verify that the FWHM of pV (x) is also H

20
The inversion of the above two expressions leads to the relations:
HL = 0:72928 + 0:19289 2 + 0:07783 3 (3.17)
H
HG = (1 0:74417 0:24781 2 0:00810 3)1=2 (3.18)
H
The dierence between the pV -functions calculated with NPROF=5 or NPROF=7
concerns only the parametrization of  and H which can be simply related to
signicant physical parameters unsing NPROF=7.
The dependence of the peak-shape parameters (including FWHM) on the
scattering variable (2 for constant wavelength diractometers) is parametrized
mainly through the variables dened in Line 11-6-1: U; V; W; X; Y; IG; SZ .
For proles NPROF=0 to NPROF=6 :
2 ) tan2  + V tan  + W + IG
H 2 = (U + DST (3.19)
cos2 
For NPROF=5 (pseudo-Voigt) the  parameter can be dependent on X
through the formula:
 = 0 + X 2 (3.20)
For NPROF=4 (tripled pseudo-Voigt), the three components are assumed to
have the same 0 and FWHM, so the eective total width depends on the
additional shape parameter Sh1 (see Line 11-8-3). The prole function is given
by the formula:

4(x) = p4 (x) = XpV (x D) + (1 X Y )pV (x) + Y pV (x + D) (3.21)
where:
D = d Scos
h1

So, apart from the FWHM that is calculated from U; V; W; DST and IG
parameters for a single component, the prole function has FOUR shape pa-
rameters 0; X; Y and Sh1 . This function is adapted for medium resolution
neutron powder diractomers having defects on the monochromator and/or
the guide spacial spectral distribution giving rise to a non-gaussian distribution
of wavelengths.
For NPROF = 6 (Pearson-VII) the m parameter can be dependent on X
and Y through the formula:
m = m0 + 100 2X + 10000 (2Y)2 (3.22)
For NPROF=7, the FWHM of the Gaussian (HG ) and Lorentzian (HL)
components is calculated as:
HG2 = (U + DST 2 ) tan2  + V tan  + W + IG (3.23)
cos2 
HL = X tan  + (Y +cosF (SZ )) (3.24)
The units of parameters U; V; W; IG are (degrees2)2. The physical meaning of
2 and F (SZ ) is brie y discussed in FULLPROF.INS.
IG ; DST
21
3.4 Monochromator, Lorentz and geometrical cor-
rections
Bragg-Brentano or Debye-Scherrer geometry
Monochromator polarization correction (CTHM and K in LINE 4); the
Lorentz polarization factor Lp is calculated as :
cos2 2Monok cos2 2
Lp = 1 K + K2 sin (3.25)
2  cos 
with CTHM =cos2 2Monok . For instance with a Graphite monochromator,
CTHM = 0.8351 and 0.7998 for CuK and CuK respectively.
Note that K is used only for synchrotron data (INSTRM=4) and does not
have to be input for other kind of data taken with the specied geometry.
 For neutrons, K =0.0.
 For characteristic X-Ray radiation (unpolarized beam), K =0.5.
 For synchrotron radiation, K must be given (K  0:1)
Transmission at-plate geometry
In the transmission geometry, at plate with the scattering vector within
the plate (Stoe geometry for X-rays, ILOR=2) the Lorentz factor is:
L = sin12 (3.26)
and the polarization correction is given by:
2 2 1 + c2 cos2 2
p = K 1 + 1c1+cos
c1 + (1 K ) 1 + c2 (3.27)
where p
c1 =j cos 2Monok j= CTHM
c2 = cos2 2Monok = CTHM
K = fraction of perfect crystal contribution
This geometry (ILOR=2) requires the use of a non-zero absorption coecient.

3.5 Asymmetry
The default asymmetry correction (see RLIM in LINE 4) follows the expression
given in [12]. The asymmetry correction adopts the form:
z) + P2 Fb (z) + P3 Fa (z) + P4 Fb (z)
Ah = 1 + P1 Fa(tan h tan 2h (3.28)
Where
z = 2i FWHM
2h Sshf

22
Sshf includes the zero-point and other shifting terms,
Fa (z) = 2z exp( z 2 ); Fb (z) = 2(2z2 3)Fa(z)
The asymmetry correction 3.28 has four independent parameters, (P1 ; P2; P3; P4)
which are read in Line 11-8-1.
If NPHASE<0 the method proposed by C.J.Howard (see [11]), is used. The
approximation of the convolution integral is performed using the Bode's rule
(Simpson's formula for ve points). The prole is calculated as a superposition
of ve prole functions g (x) (only pseudo-Voigt NPROF=5 and NPROF=7 are
implemented for this correction) calculated at displaced points:

(x) = 901 f7g (x) + 32g (x + c P ) + 12g (x + c P ) + 32g (x + c P ) + 7g (x + c P )g

2 3 4 5
(3.29)
Where x = 2i 2h Sshf , P is the asymmetry parameter and
cot 2 = 16c2 = 4c3 = 16 9 c4 = c5
The parameters P1 ; P2 normally suce for neutron diraction. The starting
value of these parameters should be signicantly lower than unity (e.g. 0.01) to
get good results. If the value of the asymmetry parameter used in the Rietveld's
formula (see [2]) is kept xed in FullProf the renement could be very bad and
couldn't converge.

3.6 Preferred orientation

Only two preferred orientation functions are currently implemented in the pro-
gram:
 NORI=0 ! the exponential function:
Ph = G2 + (1 G2 ) exp(G12h ) (3.30)
Where G1 and G2 are renable parameters and h is the acute angle
between the scattering vector and the normal to the crystallites (platey
habit). Note that setting G1 to any number >99.0 for a phase causes the
program to generate, for that phase, only those re ections for which [hkl]
is parallel to the preferred orientation vector PREF specied in Line 11-2.
 NORI=1 ! Modied March's function:
sin 2 h ! 3=2
Ph = G2 + (1 G2) (G1 cos h ) + G 2 (3.31)
1
Where G1 and G2 are renable parameters. This expression is adapted
to both ber and platey habits:

23
 { G1 < 1: Platey habit (  is the acute angle between the scattering
vector and the normal to the crystallites)
{ G1= 1: No preferred orientation
{ G1 > 1: Needle-like habit ( is the acute angle between the scatter-
ing vector and the ber axis direction)
Note that these values of G1 correspond to the Bragg-Brentano geometry of
usual X-ray powder diractometers; for the Debye-Scherrer geometry of most
neutron powder diractometers the opposite holds.
The parameter G2 represents the fraction of the sample that is not textured.
The program put its value between 0 and 1 in case of divergence.

3.7 Absorption and micro-absorption

For Debye-Scherrer data, intensities may be corrected for the eects of sample
absorption by applying the following transmission factor:
Th = expf (1:7133 0:0368 sin2 h )R + (0:0927 + 0:375 sin2 h )(R)2g
(3.32)
Where  is the linear absorption coecient and R the radius of the cylindrical
sample.
For a at plate in transmission geometry for X-rays (ILOR=2) the absorp-
tion correction is implemented as:
Th = exp( cosmt= cos h ) (3.33)
h
Where t is the eective thickness of the sample. The product mt is given in the
same place as R.
For Bragg-Brentano geometry in X-rays an angular-dependent microabsorp-
tion correction has been introduced following [24] and [25]. The factor Th
becomes:
Th ) Th Sr (h ) = Th (1 P (h )) (3.34)
Where Sr (h ) is given by the formula 6 of [24] (or P (h ) is given by formula 17
of [25]).  
P (h ) = P0Cp sin 1 sin (3.35)
h h
The limitations and degree of applicability of the above formula are ex-
plained in the cited references.

3.8 Systematic line-shifts

Powder diraction data are sometimes aected by systematic aberrations aris-
ing either from the sample itself or from an improper setting of the sample
or diractometer. FullProf gives the possibility to correct for two of the most
commonly occurring errors by rening the parameters called SYCOS and SYSIN

24
(Line 10-1). These parameters relate to errors having a cos  and sin 2 depen-
dency, respectively. The corresponding errors originate from a dierent physical
or/and geometrical problem depending on the diraction geometry. They are
summarized below:
3.8.1 Bragg-Brentano parafocusing arrangement
The two largest systematic aberrations of  2 powder diractometers oper-
ating in this geometry arise from specimen displacement and transparency; the
sample displacement error is one of the largest systematic error aecting line
positions in this geometry. It is given by:

2 = 2s cos  [in radians]
R (3.36)
where s is the displacement of the sample surface with respect to the axis of
the goniometer and R the radius of the goniometer circle. The negative sign
means that a displacement away from the center of the focusing circle moves
the diraction lines to lower 2 angle. The renable parameter is SYCOS =
2s=R. This is by far the largest systematic aberration in this geometry. As the
angles are expressed in degrees in FullProf, the sample oset can be calculated
as:  R SYCOS
s = 180
The transparency correction is given by the relation:

2 = 2R1 sin 2 [in radians] (3.37)
where  is the linear absorption coecient of the sample. This relation holds
in the case of thick absorbing samples and the renable parameter is SYSIN =
1=(2R). For thin transparent samples, the correction would write:

2 = Rt cos  [in radians] (3.38)
where t is the sample thickness; this (less usual) correction is not explicitly
included in the code but can be accounted for by the displacement correction
which turns out to show the same 2 dependency. Note however that samples
requiring that kind of correction would also give biased integrated intensities;
correction for this eect is not implemented in FullProf. For further details
on systematic aberrations in Bragg-Brentano geometry, see [16].
3.8.2 Debye-Scherrer
The largest shifts of Debye-Scherrer rings result from sample o-centering and
absorption. Eccentricity perpendicular to the incident beam direction is nor-
mally a second order eect if both sides of the Debye-Scherrer ring are measured.
If only one side of the cone is measured, the line shift takes the form:

2 = Re cos  [in radians] (3.39)

25
where e denotes the eccentricity, that is the rened parameter is SYCOS =
e=R.
Eccentricity in the incident beam direction is observed in both cases and
takes the form:

2 = Re sin 2 [in radians] (3.40)
i.e., the rened parameter is SYSIN = e=R. The correction is negative for a shift
along the beam direction towards the detector. For highly absorbing specimen
with radius r, diraction is limited to a cylindrical surface layer resulting in a
maximum peak shift:

2 = Rr cos  [in radians] (3.41)
i.e., in this case, SYCOS = r=R. The latter eect also leads to disymmetrical
line proles.
3.8.3 Curved position sensitive detector with at plate sample
For the asymmetric geometry of diractometers using a curved position sensitive
detector (CPSD) with a at-plate sample, the displacement correction takes the
form:

2 = R sine  sin 2 [in radians] (3.42)
where R is the radius of the CPS and  the incident beam angle (in de-
grees) at sample surface. Thus, the parameter rened by FullProf is SYSIN
= s=(R sin ). The negative sign means, as in the case of Bragg-Brentano ge-
ometry, that a displacement away from the center of the focusing circle moves
the diraction lines to lower 2 angle; the value of the sample oset is given by:
 R sin  SYSIN
s = 180

3.9 Crystal structure factors

The crystallographic structure factor Fh is calculated in FullProf by using the
formula:
Xn m
X
Fh = Oj fj (h ) exp( Bj j h j =4) Tjs (h ) expf2i(h T Ssr j + h T t s)g
j =1 s=1
(3.43)
where n is the number of atoms in the asymmetric unit, m is a the number
of the reduced set of symmetry operators (centering lattice translations and
inversion center operators removed). Oj is the occupation factor, fj (h ) is the
scattering length (in electron units for X-rays, in 10 12 cm for neutrons), Bj
is the isotropic temperature parameter given in  A2 , and r j is the position
vector of atom j . The symmetry operator fSs j t s g = fS j t gs is applied
to the scattering vector h (treated here as a column matrix) instead of the

26
position vector. h T is a row matrix with elements (hkl). The temperature
factor Tjs (h ) is given by:
Tjs (h ) = expf h T Ss j SsT h g (3.44)
where  j is the symmetrical matrix representing the anisotropic temperature
parameters of the atom j . For the rst atom position (Ss=1 = I ) the expression
of the anisotropic temperature factor is the well-known expression:
T (hkl) = expf (11h2 + 22k2 + 33l2 + 212hk + 213hl + 223kl)g (3.45)
where the subscript j has been droped for simplicity. Of course, if the isotropic
temperature factor Tj (iso) = exp( Bj sin2 =2 ) is used the parameters j
should be set to zero. The  's have no direct physical meaning. They have to
be converted to a cartesian U-matrix that provides, after diagonalization, the
r.m.s (root mean squares) atom displacements (see [17]). FullProf does this
work at the end of the renement, the results are given in the le CODFIL.out.
Apart from the standard scattering factor for indivual atoms existing in
an internal library of FullProf. The version 3.2 and higher can handle com-
plex form-factors as a standard option. In the general expression of the nu-
clear structure factor (see 3.43) the form factor fj (h ) is normally dependent
on the module of h . For molecular plastic crystals the treatment of rotat-
ing molecules cannot be done using an atomic description. The approach of a
molecular form-factor that takes into account the particular dynamics of the
object is more reliable. fj (h ) depends on a series of parameters for dierent
types of objects. Coecients of Symmetry Adapted Spherical Harmonics, geo-
metrical parameters (radius of a sphere, length and radius of a cylinder or disk,
etc), scattering density, for instance, could serve for describing the scattering
factor of a complex object. In the FullProf version 3.2 or higher the available
(or projected) objects are the following: spherical shell (SPHS), dense sphere
(SPHE), elipsoid (ELLI), cylinder/disk of eliptical section (DISK), etc.
For the calculation of the integrated intensities (3.2) two types of factors
are applied to Fh2 . One is an overall temperature factor (expf Bov j h j =2g)
and the other is the constant: NLAT = (LAT
ICEN )2, where LAT is the
number of centering translations (1 for P, 2 for A,B,C and I, 3 for R and 4 for
F) and ICEN =2 for centrosymmetric and ICEN =1 for non-centrosymmetric
space groups.

3.10 Magnetic scattering calculations

For a magnetic phase Fh2 is calculated using the general formula of Halpern
and Johnson:
Fh2 =j F ? (h ) j2 =j F m(h ) j2 (e
F m(h ))2 (3.46)
where F m (h ) is the magnetic structure factor, and e is the unit vector along
the scattering vector h. Here the scattering vector is written as h=H+k where
27
H is a reciprocal lattice vector of the crystal structure and k the propagation
vector corresponding to the current magnetic re ection. The magnetic struc-
tures that can be rened with FullProf must have a distribution of magnetic
moments that can be expanded as a Fourier series:
X
lj = S k j expf 2ik R lg (3.47)
fk g
In such a case the magnetic structure factor is given by:
Xnc
F m(H + k ) = p fj (H + k )S k j expf2i(H + k )r j g (3.48)
j =1
The sum is over all the atoms in the crystallographic cell. The constant p(=
re =2) is 0.2695 and allows the conversion of the Fourier components of mag-
netic moments, given in Bohr magnetons (B ) to scattering lengths units of
10 12cm. fj (H + k ) is the magnetic form factor and r j is the vector position
of atom j . In the above expression the atoms have been considered at rest.
If thermal motion is considered and if symmetry relations are established for
coupling the dierent Fourier components S k j , we obtain the general expres-
sion of the magnetic structure factor used in FullProf for the re ection with
scattering vector h= H + k :
Xn X
F m(h) = p Oj fj (h)Tj (iso) Mjs S k j Tjs expf2i[hfS j t gsr j k js]g
j =1 s
(3.49)
The sum over j concerns the atoms of the magnetic asymmetric unit for the
wavevector k (the Fourier component with index k contributes only to the k-
satellite). The sum over s concerns the dierent symmetry operators of the
crystal space group that belong to the wave vector group. The matrix Mjs
transform the components of the Fourier term S k j of the starting atom j 1
to that numbered as js in the orbit of j . The anisotropic temperature factor,
Tjs, is simplied in the calculation to only diagonal terms (), but it is not
generally necessary to use these terms in magnetic renements. The phase
factor k js has two components:
k js = k j + k js (3.50)
k j is a phase factor which is not determined by symmetry. It is a renable
parameter and it is signicant only for an independent set of magnetic atoms
which respect to another one. k js is a phase factor determined by symme-
try. The Fourier component k of the magnetic moment of atom j 1, S k j , is
transformed to
S k js = Mjs S k j expf 2ik js g (3.51)
The sign of k js changes for -k. The re ection H + k has the negative sign
indicated in the above formulae and the re ection H k has the positive sign.
In the general case S k j is a complex vector (in general there are six com-
ponents. In old versions of FullProf one could simulate this complex vector by
28
splitting the atom contributing to propagation vector k in two parts by putting
a magnetic phase k j of =2 with respect to the real part of S k j . The mag-
netic phases are given in fractions of 2 , then for the above purpose one can
use a xed Phase=0.25. In the new version this splitting is not needed. The
imaginary components are read in the place which was reserved for anisotropic
temperature factors (see Lines 11-4-3). For the scattering vector H k the
Fourier component is the complex conjugate of the Fourier component used for
calculating the structure factor for H + k . The program takes into account
automatically this fact. If k is at the interior of the Brillouin Zone a factor 1/2
is applied to the Fourier coecient.
Let us consider a single index j for all the magnetic atoms in the unit cell
as in 3.49. The Fourier coecient for the sublattice j is explicitely given by:
S k j = 12 fRxj e 1 + Ryj e 2 + Rzj e 3 + i[Ixj e 1 + Iyj e 2 + Izj e 3]g expf 2ik j g
(3.52)
The vector -k must also be given either explicitly or implicitly by giving NVK<0
(see NVK on Line 11-2 ). If NVK<0 the program applies the factor 1/2 because
it is supposed that k is non equivalent to -k even if k belong to the surface of the
Brillouin zone. If the option JHELIX=1 is used, the number of free parameters
per magnetic atom is reduced. The Fourier coecients are considered of the
form:
S k j = 21 [m1j u j + im2j v j ] expf 2ik j g (3.53)
where u j and v j are orthogonal unit vectors. If m1j = m2j the magnetic
structure for the sublattice j corresponds to a classical helix (or spiral) of
cylindrical envelope. All j atoms have a magnetic moment equal to m0 . If
m1j 6= m2j the helix has an elliptical envelope and the moments have values
between min(m1j ; m2j ) and max(m1j ; m2j ). If m2j = 0 the magnetic structure
corresponds to a modulated sinusoid of amplitude A = m1j .
In general, the user has to calculate the real magnetic moments from the
rened values of the Fourier components: the phrase "Magnetic Moment" in
the output le means the modulus of the corresponding Fourier component.
The program MOMENT has been written in order to help the user with these
calculations. In any case the calculation of the magnetic moment of the atom
j in the unit cell of index l should be done by using the formula:
X
lj = S k j expf 2ik R lg
fk g

X
lj = fR k j cos 2[k R l + k j ] + I k j sin 2 [k R l+ k j ]g
[k ]
where the last sum is extended for half the number of propagation vectors, i.e.
over the number of pairs (k,-k).

29
 If the propagation vector k is commensurate (rational components) one
can use the magnetic unit cell and S k j can be identied with the magnetic
moment at site j . In this case one can describe the magnetic structure with
k j = 0 and Q=H, being H an integer vector of the reciprocal lattice of the
magnetic cell. If k= 21 H, one can use the chemical unit cell and real magnetic
moments. In such a case only one propagation vector is needed: if NVK is
given as negative the generation of magnetic re ections could be in error. For
centered crystallographic unit cells one can use only the content of a primitive
cell and generate the satellites from the symbol of the centering followed by -1
(e.g. I -1 for a I-centered cell). In order to take the advantage of the crystal-
lographic conventions (propagation vector given with respect to the reciprocal
basis of the conventional cell) one can use the dimensions and the metrics of
the convencional cell provided that, putting the content of a primitive cell in
the conventional cell frame, the ocupation factors are multiplied by the num-
ber of centering vectors. See the les hob*.pcr in the example directory of the
anonymous FTP-area.

30
Bibliography
[1] H.M. Rietveld, Acta Cryst. 22, 151-152 (1967)
[2] H.M. Rietveld, J. Applied Cryst. 22, 65 (1969)
[3] A.W. Hewat, Harwell Report No. 73/239, ILL Report No. 74/H62S
[4] G. Malmros, J.O. Thomas, J. Applied Cryst.10, 7 (1977)
[5] C.P.Khattak, D.E.Cox, J. Applied Cryst. 10, 405 (1977)
[6] R.A. Young,D.B.Wiles, J. Applied Cryst. 14, 149 (1981)
[7] D.B.Wiles,R.A. Young, J. Applied Cryst. 15, 430 (1982)
[8] G.S.Pawley, J. Applied Cryst. 14, 357 (1981)
[9] G.S.Halpern, G.S.Johnson Physical Rewiew ?, (193?)
[10] E. Prince, J. Applied Cryst. 16, 508 (1983)
[11] C.J.Howard, J. Applied Cryst. 15, 615 (1982)
[12] J.F. Berar and * Baldinozzi, J. Applied Cryst. 26, 128 (1993)
[13] W.A. Dollase, J. Applied Cryst. 19, 267 (1986)
[14] K.D. Rouse, M.J. Cooper, E.J. York and A. Chakera, Acta Cryst.
A26, 682 (1970)
[15] A.W. Hewat, Acta Cryst. A35, 248 (1979)
[16] A.J.C. Wilson, Mathematical theory of X-ray powder diraction, Philips
Technical Library, Eindhoven (1963)
[17] B.T.M. Willis and A.W. Prior, Thermal Vibrations in Crystallography,
Cambridge University Press (1975)
[18] J.F.Berar and * Lelann, J. Applied Cryst. 24, 1 (1991)
[19] A.Antoniadis, J.Berruyer and A.Filhol, Acta Cryst. A46, 692 (1990)
[20] R.J.Hill and H.D.Flack, J. Applied Cryst. 20, 356 (1987)

31
[21] J.Rodriguez-Carvajal, M.T.Fernandez-Diaz and J.L.Martinez, J.
Physics:Cond.Matt. 3, 3215 (1991)
[22] J.Rodriguez-Carvajal, Physica B 192, 55 (1993)
[23] W.H.Press, B.P. Flanery, S.A. Teukolsky and W.T. Vetterling,
Numerical Recipes (Fortran version), Cambridge University Press, 1990.
[24] W.Pitschke, N.Mattern and H.Hermann Powder Diraction 8(4), 223
(1993)
In this paper the authors rene simultaneously all occupation numbers.
This practice should be avoided. If the calculation were exact that gives
rise to a singular matrix when the scale factor is also rened.
[25] W.Pitschke, H.Hermann and N.Mattern Powder Diraction 8(2), 74
(1993)

32
Contents
1 GENERAL INFORMATION ON FullProf 3
1.1 Purpose, references and documentation : : : : : : : : : : : : : : 3
1.2 Features of FullProf : : : : : : : : : : : : : : : : : : : : : : : : : 4
1.3 Running the program, input and output les : : : : : : : : : : : 5
1.3.1 Input les : : : : : : : : : : : : : : : : : : : : : : : : : : : 6
1.3.2 Output les : : : : : : : : : : : : : : : : : : : : : : : : : : 8
2 THE RIETVELD METHOD IN PRACTICE 10
2.1 Rietveld renement : : : : : : : : : : : : : : : : : : : : : : : : : : 10
2.2 Total-pattern tting (Prole Matching) : : : : : : : : : : : : : : 12
2.3 Hints'n tricks : : : : : : : : : : : : : : : : : : : : : : : : : : : : : 12
2.4 Trouble shooting : : : : : : : : : : : : : : : : : : : : : : : : : : : 13
2.5 Examples. Content of pcr dat:zip : : : : : : : : : : : : : : : : : : 14
3 MATHEMATICAL INFORMATION 17
3.1 Calculated prole : : : : : : : : : : : : : : : : : : : : : : : : : : : 17
3.2 Background : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : 18
3.3 Peak-shape functions : : : : : : : : : : : : : : : : : : : : : : : : : 19
3.4 Monochromator, Lorentz and geometrical corrections : : : : : : : 22
3.5 Asymmetry : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : 22
3.6 Preferred orientation : : : : : : : : : : : : : : : : : : : : : : : : : 23
3.7 Absorption and micro-absorption : : : : : : : : : : : : : : : : : : 24
3.8 Systematic line-shifts : : : : : : : : : : : : : : : : : : : : : : : : : 24
3.8.1 Bragg-Brentano parafocusing arrangement : : : : : : : : : 25
3.8.2 Debye-Scherrer : : : : : : : : : : : : : : : : : : : : : : : : 25
3.8.3 Curved position sensitive detector with at plate sample : 26
3.9 Crystal structure factors : : : : : : : : : : : : : : : : : : : : : : : 26
3.10 Magnetic scattering calculations : : : : : : : : : : : : : : : : : : 27
References 31

33